I.
Chapter 14: NMR Spectroscopy
 Origin of NMR absorption

Chemical shift values in 1 H NMR:
 Local field (generated by electrons)

Shielding/Deshielding, High/Low Field

Induced magnetic field due to

-electron systems

Equivalent hydrogens – signals appearing at same chemical shifts

Enantiotopic and Diastereotopic hydrogens

Integration of signals

Spin-spin Coupling

Freely rotating systems; 3-bond distance between hydrogens; the “n+1 rule”
 Complex coupling; systems where free rotation is restricted; the “(n+1)(m+1) rule”
II.
Chapter 19: Carboxylic Acids
 Conjugation in carboxylates
 Nomenclature
 Acid-base equilibrium; why a particular side of the equilibrium is favored
 Substituted benzoic acids; comparison of acidities
 Phenols as acids
 Separation of carboxylic acids and phenols from alcohols
III.
Chapter 20: Introduction to Carbonyl Chemistry

The reactivity of the carbonyl group
 Aldehydes/Ketones and Carboxylic Acid Derivatives

Nucleophilic addition versus nucleophilic substitution reactions to carbonyl compounds

Hydride addition to aldehydes and ketones

Stereoselective hydride addition with the CBS reagent
 Hydride substitution reactions of carboxylic acid derivatives
 LiAlH
4
–substitution then addition
 LiAlH[OC(CH
3
)
3
]
3
–only substitution: acid chloride to aldehyde
 DIBAL-H –only substitution: ester to aldehyde

Organometallic Reagents
 Organolithium Reagents: Preparation; Reactions with
1.
aldehydes and ketones (addition)
2.
acid chlorides and esters (substitution then addition)


Grignard Reagents: Preparation; Reactions with
1.
aldehydes and ketones (addition)
2.
esters (substitution then addition)
3.
epoxides
4.
carbon dioxide

Organocuprates: Preparation; Reactions with acid chlorides (to give ketones)
 Metal acetylides
 Organometallic Reagents as Bases
 Synthesis with more than one functional group: Incompatible functional groups
 A new synthetic Strategy: Protection – Deprotection
1.
Protection of a hydroxyl group by converting it into a silyl ethers
 
,

-unsaturated carbonyl compounds

Conjugate (1,4-type) additions with lithium cuprates
IV.
Chapter 21: Aldehydes and Ketones: Nucleophilic Addition
 Oxidation Reactions (to form carbonyls) –Review Section 12.12

Reversible Additions to the Carbonyl Group
 Cyanide addition – Cyanohydrin formation
 Water addition –Formation of Hydrates
 Alcohol addition –Formation of hemiacetals
 Special Nucleophiles (phosphorus ylides): The Wittig Reaction (Section 21.10: 21.10A to 21.10D)